Synthesis and crystal structure of the six-coordinate ruthenium nitrosyl complex [(η5-C5H5)Ru(PPh3)(NO)(Cl)]PF6

Conroy-Lewis, Fiona M.; Redhouse, A. D.; Simpson, Stephen J.

doi:10.1016/0022-328x(90)85495-k

Cited by 21 publications

(9 citation statements)

References 27 publications

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“…As an entry into this chemistry, the complex CpRu(PPh 3 ) 2 Cl appeared to be an attractive possibility. The complex readily undergoes substitution of a PPh 3 ligand by other two-electron donors such as CO, phosphines, phosphites, and isocyanides, and furthermore it is also possible to substitute the Cl ligand. , It was encouraging to find that the dicationic nitrosyl complexes [Cp‘Ru(PR 3 ) 2 (NO)] 2+ (Cp‘ = Cp, R = Ph or Me; Cp‘ = Cp*, R = Ph) had already been prepared by substitution of chloride in the complexes Cp‘Ru(PR 3 ) 2 Cl with the nitrosonium ion [NO] + by using [NO][BF 4 ] or [NO][PF 6 ]. ,, In view of the often parallel behavior in the reactions of nitrosonium and aryldiazonium salts, corresponding reactions with [ArN 2 ][BF 4 ] were undertaken.…”

Section: Discussionmentioning

confidence: 99%

Ruthenium Cyclopentadienyl Aryldiazenido Complexes. Synthesis of [Cp‘Ru(PR₃)₂(N₂C₆H₄OMe)][BF₄]₂and [Cp‘RuCl(PPh₃)(N₂C₆H₄OMe)][BF₄] (Cp‘ = Cp, Cp*) and X-ray Crystal Structure of [CpRu(PPh₃)₂(N₂C₆H₄OMe)][BF₄]₂, an Aryldiazenido Complex with a Large N−N−C(aryl) Angle and Near-Linear Ru−N−N−C(aryl) Skele

2000

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The neutral ruthenium complexes Cp′Ru(PR 3 ) 2 Cl [Cp′ ) Cp, PR 3 ) PPh 3 , PMe 3 , or 1/2 dppe; Cp′ ) Cp*, PR 3 ) PMe 3 ] react with [p-MeOC 6 H 4 N 2 ][BF 4 ] in acetone to give new cyclopentadienyl ruthenium aryldiazenido dicationic complexes [Cp′Ru(PR 3 ) 2 (N 2 C 6 H 4 OMe)]-[BF 4 ] 2 [Cp′ ) Cp, PR 3 ) PPh 3 (1), PMe 3 (2), or 1/2 dppe (3); Cp′ ) Cp*, PR 3 ) PMe 3 (4)] in good yields. The dicationic complexes 1-3 may also be conveniently isolated in better yield by treatment of the acetonitrile ruthenium complexes [CpRu(PR 3 ) 2 (NCMe)][BF 4 ] with the arenediazonium salt. When the reaction of Cp′Ru(PPh 3 ) 2 Cl (Cp′ 5) or Cp* ( 6)]. Further, if the reaction of Cp*Ru(PPh 3 ) 2 Cl with diazonium salt is carried out in acetone, the binuclear complex [Cp*RuCl(N 2 C 6 H 4 OMe)] 2 [Cl] 2 (7) can be isolated in low yield in addition to 6. All new complexes 1-7 were fully characterized by NMR, FT-IR, and mass spectroscopies. The structure of [CpRu(PPh 3 ) 2 (N 2 C 6 H 4 OMe)][BF 4 ] 2 ‚0.93CHCl 3 (1‚ 0.93CHCl 3 ) was determined by single-crystal X-ray diffraction. The structure exhibits a nearlinear Ru-N-N-C geometry for the coordinated aryldiazenido group, with the NNC angle having a value of 159°, compared to the "sp 2 " value of approximately 120°commonly exhibited by other "singly bent" aryldiazenido complexes. On the basis of NMR spectroscopic data, 1 reacts with NaBH 4 at low temperature to give an arylhydrazido(2-) complex [CpRu(PPh 3 ) 2 -{NN(H)C 6 H 4 OMe}][BF 4 ], which readily converts to the corresponding aryldiazene complex [CpRu(PPh 3 ) 2 (NHdNC 6 H 4 OMe)][BF 4 ] by a hydrogen shift; at room temperature, the only product is the hydrido complex CpRuH(PPh 3 ) 2 .

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Section: Discussionmentioning

confidence: 99%

Ruthenium Cyclopentadienyl Aryldiazenido Complexes. Synthesis of [Cp‘Ru(PR₃)₂(N₂C₆H₄OMe)][BF₄]₂and [Cp‘RuCl(PPh₃)(N₂C₆H₄OMe)][BF₄] (Cp‘ = Cp, Cp*) and X-ray Crystal Structure of [CpRu(PPh₃)₂(N₂C₆H₄OMe)][BF₄]₂, an Aryldiazenido Complex with a Large N−N−C(aryl) Angle and Near-Linear Ru−N−N−C(aryl) Skele

2000

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“…The dicationic Ru(II) complexes [Cp‘Ru(NO)L 2 ] 2+ (Cp‘ = Cp or Cp*; L = Lewis base) have been synthesized by a number of routes. One such route involves treatment of neutral Cp‘RuL 2 X or monocationic [Cp‘RuL 3 ] + and [Cp‘RuL 2 ] + complexes with nitrosonium salts. − Another popular method of synthesis is the reduction of the nitrite ligands in Cp‘Ru(NO 2 )L 2 complexes with protic sources. , Furthermore, the triflate ligands of Cp*Ru(NO)(OTf) 2 can be displaced by bidentate L 2 ligands to generate [Cp*Ru(NO)L 2 ] 2+ . The phenazine derivative [Cp*Ru(NO)(dppz)] 2+ (dppz = dipyrido[3,2- a :2‘,3‘- c ]phenazine) is particularly interesting since it intercalates DNA with a binding constant of >10 6 M -1 …”

Section: 22 Organometallic Complexesmentioning

confidence: 99%

“…One such route involves treatment of neutral Cp′RuL 2 X or monocationic [Cp′RuL 3 ] + and [Cp′RuL 2 ] + complexes with nitrosonium salts. [933][934][935][936][937][938][939] Another popular method of synthesis is the reduction of the nitrite ligands in Cp′Ru(NO 2 )L 2 complexes with protic sources. 934,940 Furthermore, the triflate ligands of Cp*Ru(NO)(OTf) 2 can be displaced by bidentate L 2 ligands to generate [Cp*Ru(NO)L 2 ] 2+ .…”

Section: Organometallic Complexesmentioning

confidence: 99%

Coordination and Organometallic Chemistry of Metal−NO Complexes

2002

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“…The dark red product isolated (85% yield) was found to be [Ru(NO-phpy)([9]aneS3)(CH 3 CN)] 2+ ( 2-CH 3 CN ; NO-phpy = 2-(2-nitrosophenyl)pyridine) by 1 H and 13 C NMR spectroscopy, X-ray crystallography, and elemental analysis (Scheme ). This reactivity is different from that for other ruthenium(II) complexes which react with NO + substitutionally to give the ligand-substituted Ru−nitrosyl products. ,,,, Reaction between the S-bound dmso complex [Ru(phpy)([9]aneS3)(dmso)] + ( 1-dmso ) and [NO][BF 4 ] in CH 3 CN also gave 2-CH 3 CN in 80% yield.…”

mentioning

confidence: 90%

“…R−M−(NO) + L → L−M−N(O)R, has been demonstrated to be a critical step in carbon−nitrogen bond formation. Nitrosonium ion (NO + ), a close relative of NO, is known to react substitutionally with metal complexes to give metal−nitrosyl systems, ,− although there are several examples proposing that NO + can insert into metal−carbon bonds in an intermolecular fashion. − , We herein present a systematic investigation of the reaction between NO + and 2-phenylpyridine anion (phpy)-ligated cyclometalated ruthenium(II) complexes, which demonstrates for the first time that NO + inserts into a Ru II −aryl phpy bond to give 2-(2-nitrosophenyl)pyridine (NO-phpy)-coordinated complexes. Experimental evidence supports a direct bimolecular NO + insertion mechanism, i.e.…”

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confidence: 96%

Facile Direct Insertion of Nitrosonium Ion (NO⁺) into a Ruthenium−Aryl Bond

et al. 2011

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T he discovery that nitric oxide plays many fundamental physiological roles has aroused interest in the structures, electronic properties, and reactivities of metal-nitrosyl complexes. [1][2][3][4][5][6][7][8][9][10][11][12][13] The chemistry between NO and organometallic complexes, especially reactions that lead to formation of new carbonnitrogen bonds, is of considerable interest because organic nitroso compounds have been demonstrated to be a class of attractive electrophiles in many carbon-nitrogen and/or carbon-oxygen bond forming reactions. 14-20 In the past few decades, investigations on the insertion of NO into metal-alkyl and metal-aryl bonds to form C-nitroso complexes provided insightful results for the development of metal-mediated organic transformation reactions, 21-36 and the alkyl/aryl moiety migration to the coordinated NO ligand, i.e. R-M-(NO) þ L f L-M-N(dO)R, has been demonstrated to be a critical step in carbon-nitrogen bond formation. Nitrosonium ion (NO þ ), a close relative of NO, is known to react substitutionally with metal complexes to give metal-nitrosyl systems, 8,37-44 although there are several examples proposing that NO þ can insert into metal-carbon bonds in an intermolecular fashion. [25][26][27]31 We herein present a systematic investigation of the reaction between NO þ and 2-phenylpyridine anion (phpy)-ligated cyclometalated ruthenium(II) complexes, which demonstrates for the first time that NO þ inserts into a Ru II -aryl phpy bond to give 2-(2-nitrosophenyl)pyridine (NO-phpy)-coordinated complexes. Experimental evidence supports a direct bimolecular NO þ insertion mechanism, i.e. M-R þ NO þ f [M-N(dO)-R] þ , but not an intramolecular migratory insertion mechanism for the insertion reactions in this work. Moreover, theoretical calculations reveal that direct NO þ insertion into the Ru-C bond may be rationalized as a frontier orbital interaction between the [Ru-aryl]-based HOMO of the Ru(II) complexes and the LUMO of the NO þ . Unlike many literature examples, the non-NO-ligated complexes [Ru(phpy)([9]aneS3)(L)] þ ([9]aneS3 = 1,4,7-trithiacyclononane) were employed to react with NO þ in this study; this can reduce ambiguity in mechanism evaluations. When excess [NO][BF 4 ] (5-fold) was added to [Ru(phpy)([9]aneS3)(solv)] þ (1-solv; solv = CH 3 CN, EtOH) in CH 3 CN under argon at room temperature, the solution changed from yellow to dark red immediately. The dark red product isolated (85% yield) was found to be [Ru(NO-phpy)-([9]aneS3)(CH 3 CN)] 2þ (2-CH 3 CN; NO-phpy = 2-(2-nitrosophenyl)pyridine) by 1 H and 13 C NMR spectroscopy, X-ray crystallography, and elemental analysis (Scheme 1). This reactivity is different from that for other ruthenium(II) complexes which react with NO þ substitutionally to give the ligand-substituted Runitrosyl products. 37,38,40,41,43 Reaction between the S-bound dmso complex [Ru(phpy)([9]aneS3)(dmso)] þ (1-dmso) and [NO]-[BF 4 ] in CH 3 CN also gave 2-CH 3 CN in 80% yield.The X-ray crystal structure for [2-CH 3 CN](PF 6 ) 2 3 CH 3 CN represents the...

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Synthesis and crystal structure of the six-coordinate ruthenium nitrosyl complex [(η5-C5H5)Ru(PPh3)(NO)(Cl)]PF6

Cited by 21 publications

References 27 publications

Coordination and Organometallic Chemistry of Metal−NO Complexes

Facile Direct Insertion of Nitrosonium Ion (NO⁺) into a Ruthenium−Aryl Bond

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Synthesis and crystal structure of the six-coordinate ruthenium nitrosyl complex [(η5-C5H5)Ru(PPh3)(NO)(Cl)]PF6

Cited by 21 publications

References 27 publications

Coordination and Organometallic Chemistry of Metal−NO Complexes

Facile Direct Insertion of Nitrosonium Ion (NO+) into a Ruthenium−Aryl Bond

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Facile Direct Insertion of Nitrosonium Ion (NO⁺) into a Ruthenium−Aryl Bond